Recording member of photocolor developing and eliminating material and the recording method

ABSTRACT

This invention provides a photocolor developing and eliminating composition, a recording member of monochrome or multicolor developing and eliminating composition, method for image forming, fixing, or restoring which is applicable to said recording members and usual recording members of photocolor developing and eliminating material, and method for projecting image on a screen of photocolor developing and eliminating material. A photocolor developing and eliminating composition comprises a photocolor developing and eliminating material and a stabilizer, which is either electron or proton donating or accepting material or solid matter, on which surface said material being dispersed and which inherently possesses acidic, basic, ionic, electric charge transferring or high surface energy property at the surface, and the stabilizer stabilizing the color-developed state continuously, restoring after fixing the color-developed state to the colorless state by the stimulus of radiation having another range of wave length and reproducing a stable color-development. The multicolor developing and eliminating composition comprises a film matter prepared by incorporating a photocolor developing and eliminating material to a transparent or translucent dispersion medium or the film attaching to a support such as paper and the like, and the recording member is wholly color-developed by irradiating it by a radiation having at least one range of wavelength such as light, heat and the like. Particularly, at least one dispersion medium is used to cover the whole visible light range in the colored state. And the color image recording method is very useful for the rapid, simple and much memorizing and recording in information industry such as communication, measurement, documentation and display.

United States Patent 1191 llnoue et al.

1451 Sept. 30, 1975 [75] Inventors: Eiichi Inoue, Tokyo; Isamu Shimizu,

Fuchu, both of Japan [73] Assignee: Canon Kabushiki Kaisha, Tokyo,

Japan 22 Filed: Jan. 22. 1973 211 Appl. No: 325,304

Related U.S. Application Data [63] Continuation of Ser. Nov 705,758,Feb. 15, 1968, abandoned, which is a continuation-inpart of Ser.

No. 630,519, April 1, 1967, abandoned.

[30] Foreign Application Priority Data Apr. 14, 1966 Japan 41-23217 May31, 1967 Japan... 42-35075 Feb. 20, 1967 Japan 42l1070 [52] U.S. CI96/452; 96/48 R; 96/90 PC [51] Int. Cl.- G03C 5/32; 603C 1/52 [58] Fieldof Search 96/90 PC. 48, 45.2

[56] References Cited UNITED STATES PATENTS 3,134,674 5/1964 Brown 96/903,361,706 1/1968 Smith..... 3,667,949 6/1972 Inoue 96/90 PC FOREIGNPATENTS OR APPLICATIONS 658,273 6/1965 Belgium 96/90 OTHER PUBLICATIONSASD-TR 61-70 page 356.

Primary E.\'aminerNorman Gv Torchin Assistant Examiner-John L. GoodrowAttorney, Agent, or FirmFitzpatrick, Cella, Harper & Scinto I [57]ABSTRACT This invention provides a photocolor developing and eliminatingcomposition, a recording member of monochrome or multicolor developingand eliminating composition, method for image forming, fixing, orrestoring which is applicable to said recording members and usualrecording members of photocolor develop ing and eliminating material,and method for projecting image on a screen of photocolor developing andeliminating material. A photocolor developing and eliminatingcomposition comprises a photocolor de-' veloping and eliminatingmaterial and a stabilizer, which is either electron or proton donatingor accepting material or solid matter, on which surface said materialbeing dispersed and which inherently possesses acidic, basic, ionic,electric charge transferring or high surface energy property at thesurface, and the stabilizer stabilizing the color-developed statecontinuously, restoring after fixing the color-developed state to thecolorless state by the stimulus of radiation having another range ofwave length and reproducing a stable color-development. The multicolordeveloping and eliminating composition comprises a film matter preparedby incorporating a photocolor developing and eliminating material to atransparent or translucent dispersion medium or the film attaching to asupport such as paper and the like, and the recording member is whollycolor-developed by irradiating it by a radiation having at least onerange of wavelength such as light, heat and the like. Particularly, atleast one dispersion medium is used to cover the whole visible lightrange in the colored state, And the color image recording method is veryuseful for the rapid, simple and much memorizing and recording ininformation industry such as communication, measurement, documentationand display.

11 Claims, 8 Drawing Figures US. Patent Sept. 30,1975

FIG.IA FIG.|B

Sheet 1 of 4 FIG. Ic

FIG. 2

A,B, C THREE LAYERS I 400 soo 600 100011;!)

FIG. 4

POSITIVE COLOR IMAGE FIG. 5b

N-SALICYLIDENE -m- TOLUIDINE 400 s00 00 7OOImpI FIG.3

POSITIVE COLOR SLIDE FIG. 5a

CINNAMIC ALDEHYDE SEMICARBAZONE (MICRO CRYSTALLINE) 4 500 so 700mm FIG.5c

N 4'METI-IYLSALICYLI- DENE ANILINE US. Patent Sept. 30,1975 Sheet 2 of43 909266 COOH FIG. 59- FIG. 56-2 FIG. 58-3 ACETONE SOLU- METHYLALCOHOLPROPYLALCOHOL TION SOLUTION SOLUTION r I I x l I \l I k l 400 500 600700(mpl 400 500 600 700mm 400 500 600 700(01):)

FIG. 5f FIG. 5M

6', a,- D|BROM0-l,3,3- N,N- DIMETHYL- TRIMETHYLINDOLINO- FORMAMIDESOLUTION BENZOPYRYLSPIRAN. ME!

I Br

FIG. 5f-2 METHYLALCOHOL SOLUTION FIG 59 6' NITRO- 8'- METHOXY 1,3,3-TRIMETHY LINDOLINO- BENZOPYRYLSPIRAN.

CH3O

N02 400 500 600 700mm) US. Patent Sept. 30,1975 Sheet 4 of4 3,909,266

FIG. 6

FIG.7

FIG. 8

RECORDING MEMBER OF PHOTOCOLOIR DEVELOPING AND ELIMINATING MATERIAL ANDTHE RECORDING METHOD This is a continuation of U.S. application Ser. No.705,758, filed Feb. 15, 1968, now abandoned, which in turn is aContinuation-ln-Part of U.S. application Ser. No. 630,5 l9, filed Apr.1, 1967, and now abandoned.

This invention relates to a recording technique in which a photocolordeveloping and eliminating material is used. More particularly, thisinvention relates to a novel recording members of monochrome ormulticolor photocolor developing and eliminating material, methods forcolor-developing, fixing and restoring which are applicaable to saidrecording members and usual recording members of photocolor developingand eliminating material, and image projecting methods in which novelscreens comprising photocolor developing and eliminating material areused.

Heretofore, photosensitive materials used in conventional recording,photographic or copying technique are such that a latent image is formedon said photosensitive material by exposure, developed by chemical orphysical means and then fixed to form stable images. In such prior art anumber of processes are necessary to form the image, and a fairly largeapparatus and consumption materials are required. In addition, thetreating speed is disadvantageously slow.

in conventional photographic techniques such as the silver saltphotography, the diazo photography, the thermal photography,electrophotography and the like, the image formation is carried outaccording to the abovementioned processes. Among these processes, thereis seldom a process in which a once formed stable image is eliminatedand the same photosensitive surface is again exposed to form an image. Aconventional recording material by which a photosensitive surface isexposed to light to form an image thereon and the image is theneliminated followed by new exposure to form another image is aphotochromic material.

A photochromic material is generally converted to the colored state byirradiating a radiation having a specified wave length or a specifiedenergy (including rays of wave length in the range of infrared orultraviolet ray etc., hereinafter comprehensively called radiation) andthe formed color is eliminated by the stimulus of heat or light havingdifferent wave length or radiation having different energy. When thephotochromic material is used as a material for a recording member, therecording member is exposed to a radiation having a specified range ofwave length to form colored images and then another radiation having arange of wave length different from the previous one is applied toeliminate all of or a part of the colored images. Thus, the recordingmember is ready for reexposure. As mentioned above, a recording membercomprising a photochromic material can effectively reproduce variousimages repeatedly on the same recording member.

However, the conventional photochromic substances (hereinafter calledphotocolor developing and eliminating material) can not remain lastinglyin the colored state for a long time. Therefore, when a photochromicmaterial is used as a material of a recording member, an image which isstable for a long time is not obtained.

In order to solve such problem, heretofore, a photocolor developing andeliminating material has been irradiated with a radiation to develop acolor and the colored state thus formed has been simply stabilized.However, such stabilizing treatment makes the elimination of the oncestabilized image difficult as in case of the printing-out photographyand deteriorates the photocolor developing and eliminating property.Thus, the repeating recording by the same recording member is notpossible.

The color-developing mechanism of photocolor developing and eliminatingmaterials is not yet fully understood. However, the presently knownphotocolor developing and eliminating materials are considered todevelop the color by a change such as photo-ion dissociation, photohydrogen transmission, photo radical dissociation, photo stericstructure change, photooxidation, photoreduction and the like caused byirradiation of light (radiation).

According to this invention, a photocolor developing and eliminatingmaterial system and a stabilizer coexist to stabilize thecolor-developed state continuously, restore the color-developed state tothe colorless state by the stimulus of radiation having another range ofwave length and reproduce a stable colordevelopment. The photocolordeveloping and eliminating material systems include those which developcolor by a change such as photo-ion dissociation, photo radicaldissociation, photo hydrogen transmission, photo steric structurechange, photooxidation, photoreduction and the like. The stabilizer is amaterial system which stabilizes the color-developed state, eliminatesthe stabilized state by a stimulus of radiation having the other rangeof wave length to restore to the original colorless state. Thestabilizer is a material system having a property of electron or protondonating or accepting which copes with atoms, atom groups, freeradicals, ions etc. generated by the color-developing mechanism involvedin color-developed state of the photocolor de veloping and eliminatingmaterial.

The stabilizing mechanism of the stabilizer is not yet clarified, but itis probably considered that the atoms, atom groups, free radicals, ionsetc. generated as above are stably retained without causing a reversiblereaction by the electron or proton donating or accepting reaction withthe stabilized and as the result the colordeveloped state of thephotocolor developing and eliminating material is stabilized. Thus, anovel recording member which can produce stable colored images isobtained by incorporating the photocolor developing and eliminatingmaterial and the stabilizer to the photosensitive layer of the recordingmember.

The photocolor developing and eliminating material and the stabilizer asmentioned above are homogeneous system materials. When the stabilizer isdissolved in a dispersion medium together with the photocolor developingand eliminating material, the stabilizer is dissolved therein in themolecular state and assumes a property of electron or proton donating oraccepting. The stabilizer in the molecular state effects the electron orproton donating or accepting action with the atoms, atom groups, freeradicals, ions or the like produced in the color-developed state of thephotocolor developing and eliminating material. As the result, thestabilization is effected.

While the above mentioned stabilizer is composed of a material ofhomogeneous system, according to an additional aspect of this inventiona heterogeneous material or an intermediate material is also effectivelyused as a stabilizer for the photocolor developing and eliminatingmaterial. The stabilizers of a heterogeneous material or intermediatematerials are heterogeneous system materials, the surface of solidparticles of which are acidic, basic, ionic, of electric chargetransferring or of high surface energy, or the particle surface of whichis treated so as to assume such property as mentioned above. Examples ofthe stabilizers include solid acids, solid bases, sizing agents, ionicsolid and the like. The photocolor developing and eliminating materialmay be bonded to the solid particle surface of the stabilizer by simplycontacting or using a binder.

In general, the heterogeneous system material is in a form ofparticle-like solid at a usual state. Therefore, the heterogeneoussystem material can not exist in a molecular state together with thephotocolor developing and eliminating material while the stabilizer ofelectron or proton donating or accepting material can be present in amolecular state. The heterogeneous system material is not dissolved in adispersion medium in a molecular state, but dispersed in the medium in astate of solid particle. Therefore, the stabilizing mechanism of theheterogeneous system material is different from that of the homogeneoussystem material. The solid particle itself of the heterogeneous systemmaterial should have a stabilization effect. According to the presentinvention, a heterogeneous system material, the solid particle surfaceof which intrinsically possesses a tendency of stabilizing thephotocolor developing and eliminating material is selected as astabilizer. Examples of such material include materials which surface isacidic, basic, ionic, of electric charge transferring, or of highsurface energy. The photocolor developing and eliminating material isuniformly bonded to the surface of the solid particle of the stabilizerby contacting or using a binder to stabilize the photocolor developingand eliminating material in the color developed state.

Alternatively, the particle surface of the heterogeneous system materialis subjected to a stabilizing treatment in advance so as to impartacidic property, basic property, ionic property, electric chargetransferring property or high surface energy thereto, and then theparticle surface thus treated is homogeneously coated with thephotocolor developing and eliminating material by, for example,contacting or using a binder to produce a novel and stable photocolordeveloping and eliminating member having a stable color-developed stateand retaining the photocolor developing and eliminating property.Particularly, when the photocolor developing and eliminating materialcontacted with the particle surface is impregnated with a stabilizer ofa homogeneous system material such as an electron or proton donating oraccepting material as mentioned above, a remarkably stable photocolordeveloping and eliminating material is produced.

In other words, according to the aspect of this invention in which aheterogeneous system material is employed as a stabilizer, the surfaceof the stabilizer particle which has inherently acidic property, basicproperty, ionic property, electric charge transferring property and highsurface energy or the surface of the stabilizer particle which issubjected to the treatment for imparting to the surface the acidicproperty, basic property, ionic property, electric charge transferringproperty or high surface energy, is contacted with or coated with thephotocolor developing and eliminating material alone or the photocolordeveloping and eliminating material to which an electron or protondonating or accepting material is incorporated as a stabilizer. Thus,the color-developed state of the photocolor developing and eliminatingmaterial is continuously stabilized and can be restored to the colorlessstate by a stimulus of a radiation having the other range of wavelength.

The stabilization means of the photocolor developing and eliminatingmaterial as mentioned above may be applied to the fixing and chemicalelimination of the color-developed image, the color image recordingmember, or the color image recording method as mentioned later. It ispossible to obtain clear contrast, excellent half tone images as well asline images. The images may be erased or modified if desired. Further,the recording member and the recording process may be used in multipleuses. The recording member in which the photocolor developing andeliminating material stabilized in accordance with the present inventiongives stable color-developed images, and the fixing and chemicalelimination of the colordeveloped image as described later isestablished. Therefore, the recording member and the recording processof this invention may find remarkable uses in the fields of calculation,translation, communication, documentation or the other variousinformation treating systems for recording, accumulation, modification,erasing and layout of the information.

It is an object of this invention to provide novel photocolor developingand eliminating matters in which the unstable color-developed state ofphotocolor developing and eliminating materials is stabilizedcontinuously and the color-developed state can be eliminated by aradiation having the other range of wave length, i.e. the reversibilityof photocolor developing and eliminating property is still retained.

It is a further object of this invention to provide novel recordingmembers which can produce the colordeveloped images stabilizedcontinuously.

The above-mentioned various stabilizing means can retain thecolor-developed stage of image for from several ten minutes to severalten hours, but the developed color image is not kept as an everlastingimage.

According to a further aspect of this invention, the color developedstate of the photocolor developing and eliminating material is retainedas an everlasting image, that is, fixed, and further the lasting imagethus produced is restored to the original state in which the materialassumes the photocolor developing and eliminating property.

Heretofore, a fixing and restoring method has not yet known by which thecolor-developed image of the photocolor developing and eliminatingmaterial is fixed as an everlasting image and then the fixed image isrestored to the original stage where the material prosesses thephotocolor developing and eliminating property. According toconventional methods, when the color-developed image is once fixed as aneverlasting image, for example, in the printing-out photography, it isnot possible to restore the material to the original state where thephotocolor developing and eliminating property is restored again.According to the method of this invention, the fixing is carried out bytreating the photocolor developing and eliminating recording member inthe color-developed state with a basic material or an anion. Thecolor-developed image is converted to a latent image, for example, whenthe photocolor developing and eliminating material is a spiropyrancompound, the color-developed image is changed to a yellow latent imagestate. The mechanism is not yet fully understood, but it is consideredthat the atom, atom group, free radical or the like produced in thephotocolor developing and eliminating material in the colordevelopedstate is combined with the basic material to form a certain stablechemical complex which is everlastingly retained as the yellow latentimage.

Further, with respect to the restoring method, the fixed image istreated with an acidic material (cationic treatment). It is consideredthat this treatment neutralizes a certain chemical complex salt forminga yellow latent image and the basic material as the fixing agent iseliminated to form a colored image having photoreversibility.

It is a further object of this invention to provide a process comprisingfixing as an everlasting stable image a color-developed image of arecording member including singly a photocolor developing andeliminating material, a recording member including a photocolordeveloping and eliminating material to which a stabilizer isincorporated, or a recording member which is prepared by contacting orcoating the surface of particles of a heterogeneous system material,which itself has inherently the stabilizing activity or is subjected toa stabilizing treatment, with a photocolor developing and eliminatingmaterial.

Also, it is a further object of this invention to provide a restoringprocess which comprises restoring the fixed image to the originalphotocolor developing and eliminating state thereby the materialassuming a photoreversibility.

It is a further object of this invention to develop the applicationfields of the recording member by imparting the everlasting property tothe color-developed visible image and, if desired, by reverting thecolordeveloped image to the original photocolor developing andeliminating state.

In view of the special properties of the recording member comprising aphotocolor developing and eliminating material and the stabilization,fixation, and restoration thereof, various novel reproduction methodsare provided.

According to a further aspect of this invention, a nor mal image or areverse image can be optionally formed on the same recording member byusing a recording member comprising a photocolor developing andeliminating material according to a simple process.

Heretofore, a reverse image has been produced often by a wet process ofchemical procedure and the stability of procedure has not beensatisfactory, and moreover a fairly large scale apparatus and a lot ofconsumption materials are required. In addition, the treating speed isdisadvantageously slow.

According to this invention, the inherent properties of photocolordeveloping and eliminating materials are utilized to form a reversecolor-developed image by irradiating a recording member comprising aphotocolor developing and eliminating material through an originalpattern by a radiation having a specific range of wave length, or toform a normal image by uniformly color-developing the whole surface ofthe recording member and irradiating the recording member by a radiationhaving the other range of wave length. Therefore. the method of thisinvention enables to form simply and rapidly a desired normal image anda desired reverse image on the same recording member. With respect tothe formation of the reverse color-developed image on the recordingmember, a radiation having wave length ranges corresponding to thecharacteristic absorption ranges of a photocolor developing andeliminating material in the recording member is projected to therecording member through an original pattern to bring the recordingmember to a color-developed state having the range of absorption wavelength in visible light region. If the original pattern is negative inthe above case, a positive color-developed image, i.e. a reverse image,is obtained since the radiation is projected to the portion of therecording member corresponding to the image parts of the originalpattern. On the contrary, with respect to the formation of a normalimage on the recording member, a radiation having the ranges of wavelength correspondng to the characteristic absorption wave length regionof the photocolor developing and eliminating material in the recordingmember is projected to the recording member to color-develop uniformlythe whole surface of the recording member, and then the color-developedrecording member is irradiated by a radiation having the other range ofwave length through a positive original pattern to eliminate theportions of the recording member other than portions corresponding tothe original pattern. As the result, a positive color-developed image isformed. Further, the whole surface is color-eliminated and irradiatedagain by a radiation having the above-mentioned specified range of wavelength through a negative original pattern to form a positive reverseimage on the recording member. As mentioned above, a normal image orreverse image is optionally obtained'by the same re cording member.Further, a repetition is possible which eliminates the recorded image bylight, restores to the original wholly color-developed state, andrecords again. Further, a recording member formed by the combination ofspirans may be treated with, for example, aliphatic amines such ashexylamine, or a strong alkaline solution such as that of potassiumhydroxide to stabilize the image everlastingly in a stage of yellowlatent image, and then treated with organic acids or inorganic acids torestore the image to the original colored image.

It is a further object of this invention to provide a novel and simpleprocess for forming optionally a normal image or a reverse image rapidlyon the same recording member by using a recording member comprisingphotocolor developing and eliminating material.

There are various conventional processes for recording colored images.For example, in the known silver salt methods, a color image exposing iscarried out and further a color-developing step involving the reductionof the silver salt is necessary. In electrolytic electrophotography, anelectrolytic color-developing step is employed, and in diazo methods acoupling colordeveloping method is employed. However, these prior artsinvolve a wet type of chemical reaction and lack in the stability ofprocedure. In addition, the prior arts necessitate a fairly large scaleof apparatus and a lot of consumption materials and further the treatingspeed is disadvantageously slow.

According to the present invention, a novel color recording member basedon a novel color recording process is provided. Said recording membercomprises a film like matter itself prepared by incorporating aphotocolor developing and eliminating material to a transparent ortranslucent dispersion medium, or said film like matter attached to asupport such as paper, transparent support and the like. The recordingmember is wholly color-developed by irradiating it by a radiation havingat least one range of wave length such as light, heat, a combination oflight and heat, and the like. Particularly, at least one dispersionmedium is used to cover the whole visible light range in the coloredstate since the combination of the different absorption wave lengthranges caused by each combination of the photocolor developing andeliminating material with the different dispersion mediums may cover thewhole visible light range. Alternatively, at least one photocolordeveloping and eliminating material is selected in such a manner thateach of the material has each different individual absorption spectrumin the colored state and the combination of the material shows thephotocolor eliminating property at the visible light range.

This is explained further in detail below. In general, it is necessaryto construct a color recording member in such a manner that the colorrecording member has the absorption region or the color-developingregion over the whole visible light range. According to this invention,the recording member is constructed so that it shows the absorption overthe whole visible light range.

1. In general, the photocolor developing and eliminating material showsthe characteristic absorption in ultraviolet wave length range orinfrared wave length range before the photocolor developing andeliminating material is color-developed. Therefore, when these materialsare irradiated by, for example, a radiation of wave length ofultraviolet region, it becomes a colordeveloped state having theabsorption wave length range at the visible light range. And the colordepends on the type of the photocolor developing and eliminatingmaterial. The first type of color recording member of this inventioncomprises at least one photocolor developing and eliminating materialwhich is selected in such a manner that the material has the absorptionwave length range over the whole visible light range, and the materialis mixed and made into a layer.

2. The absorption wave length range in the colordeveloped state can bechanged by dissolving the photocolor developing and eliminating materialand changing the dispersion medium in which the material is dispersed ina matrix state. The second type of color recording member comprises thephotocolor developing and eliminating material dispersed in at least onedispersion medium in a matrix state, the photocolor developing andeliminating material being combined with the dispersion medium in such amanner that the photocolor developing and eliminating material has theabsorption wave length range over the whole visible light range at thecolor developed state and the photocolor developing and eliminatingmaterial combined with the dispersion medium being coated to form amultiple layer.

In this case, when the additive such as stabilizer as mentioned above isincorporated to the dispersion medium, the absorption wave length rangeof the photocolor developing and eliminating material in the visiblelight range can be somewhat changed in the color developed state.Therefore, when an appropriate dispersion medium and an additive areused in combination, it is possible that one and the same photocolordevelop ing and eliminating material has the absorption wave lengthrange over the whole visible light region in the color developed state.In other words, the photocolor developing and eliminating material isappropriately dispersed in a dispersion medium in which an additive isincorporated, and different dispersion mediums are employed to form amultiple layer. Thus, the combina tions of the dispersion mediums andthe photocolor developing and eliminating material enable to provide acolor recording members that the absorption range covers the wholevisible light range in the colordeveloped state.

3. In 1 and 2 above, a combination of two or more photocolor developingand eliminating materials having each different absorption wave lengthranges at the color developed state can cover the whole visible lightrange. Or, the same photocolor developing and eliminating material isused together with different dispersion mediums to which an additive maybe or not incorporated, and at least one of them is arranged as amultiple layer to form a color recording member having the absorptionwave length range covering the whole visible light range.

Further, the combination of l and 2 also provides a recording member. Inother words, the absorption wave length range of the photocolordeveloping and eliminating material in the color-developed state can beeasily changed by appropriately selecting the photocolor developing andeliminating material, the dispersion medium and the additive. Therefore,at least one of them having each different absorption wave length iscombined to provide a color recording member having the absorption wavelength range covering the whole visible light range.

Therefore, the recording member is irradiated by a radiation having atleast one specific wave length range to color-develop and then a colororiginal image pattern is projected to the color-developed recordingmember by using a radiation having the different wave length range toeliminate the developed color of the photocolor developing andeliminating material in the recording member in accordance with thecolor pattern of the color original image. Thus, a positive colorreferring to the original image is directly formed and recorded.

Particularly, in the above-mentioned color recording member thephotocolor developing and eliminating material is formed in a layerstate in accordance with the dispersion medium, for example, in threelayers. However, it is not always necessary to form a multiple layer.Alternatively, it is also possible that each of photocolor developingand eliminating materials or a mixture of each of them with a dispersionmedium is finely divided and each of the resulting finely dividedphotocolor developing and eliminating is homogeneously mixed and formedin one layer.

Further, a color image formed in the color recording member may bechanged to a yellow latent image and stabilized lastingly by treatingwith an alkali or base. If necessary, the stabilized latent image may berestored to the original color image by an acid treatment.

The color image recording method of the present invention is very usefulfor the rapid, simple and much memorizing and recording in informationindustry such as communication, measurement, calculation, documentationand display. Further, it is also useful as monitors in color imagetreating systems.

It is a further object of this invention to provide a method forproducing directly a record of color image by exposing an imagerecording member to a color image projection. The purpose of thisinvention is to provide a novel color recording member which utilizes aphotocolor developing and eliminating material.

It is a further object of this invention to provide a method whichcomprises using one and the same color recording member, forming a colorimage directly on the recording member, eliminating the color image by aradiation having at least one wave length range such as light, heat anda combination of light and heat, and thus forming a color imagerepeatedly on one and the same recording member.

It is a further object of this invention to provide a method whichcomprises fixing a color image produced on the novel color developingmember to convert the color image to an everlasting stable image in alatent image state and, if necessary, restoring the latent image to theoriginal color image.

It is a further object of this invention to provide a novel imageformation by projection in which a photocolor developing and eliminatingmaterial and a novel reproduction method are employed.

It is a further object of this invention to provide a novel projectionmethod which comprises using a novel screen comprising a photocolordeveloping and eliminating recording member and forming optionally anormal image and a reverse image.

In conventional projection methods, a reverse image is prepared inadvance and projected. However, the method for obtaining the reverseimage necessitates often wet type steps of chemical reactions taking along time and the procedure stability is low. Further, the methodnecessitates a fairly large scale apparatus and much consumptionmaterials and the procedure is complex. Further, in the conventionalprojection method a dark room is necessary to enchance the contrast ofthe projected image.

This invention provides a novel method of projecting images which uses ascreen prepared by dispersing a photocolor developing and eliminatingmaterial alone or a photocolor developing and eliminatingmaterial towhich the previously mentioned material is added, if necessary, a binderbeing added thereto, in a liquid matrix such as benzene, toluene and thelike, or in a high polymer dispersion medium, and forming a film fromthe resulting dispersion. Alternatively, the screen may be prepared bycoating the dispersion of the photocolor developing and eliminatingmaterial on a support such as resin, glass, metal, paper, fiber, wood,porcelain and the like.

In this method of this invention, a method for forming a normal image ora reverse image by using one and the same recording member is applied toan image projecting method such as a slide projection, a cinema and thelike. In the novel image projection method of this invention, in casethat a reverse image projection is obtained by using a screen comprisinga photocolor developing and eliminating material, the photocolordeveloping and eliminating material is usually colordeveloped by anappropriate exciting light such as ultraviolet light and the likeenabling to form an absorption range in the visible light region. Whenthe negative film is irradiated by an appropriate exciting light, theexciting light does not pass through the dark parts of the negative filmand the corresponding part on the screen hardly color-develops while theexciting light passes the light part or the transparent part and thecorresponding part on the screen color-develops.

Thus, a positive image is obtained from a negative film.

This image exists only while the exciting light is projected, and whenthe exciting light is removed, the image is eliminated. Therefore, themethod as mentioned above can be utilized in the projection of cinefilmas well as the projection of slide-film. When a screen is made from amaterial giving an after image, it is not always necessary to projectcontinuously an exciting light. Further, it is effective to project avisible light to a screen for the purpose of accelerating theelimination of the after image or irradiating the screen.

On the contrary, in order to obtain the normal image projection, analready color-developed matter in the visible light range or a matterwhich has been colordeveloped by a stimulus of light other than visiblelight, a stimulus of heat and the like, is exposed to a visible light toeliminate the image, and thereby a normal image projection is obtained.

When the matter is not yet color-developed in a visible light range, itis necessary to color-develop uniformly the whole surface in a visiblelight range by applying a color-developing means inside of the screen,or from the front or the behind of the screen. When a visible light isprojected through a positive film to the already color-developed screenor the screen colordeveloped by a certain color-developing means, adeveloped color at a portion of screen corresponding to a portion of thefilm which the visible light passes through, is eliminated to give apositive image projection.

It is a further object of this invention to provide a projected imageforming process such as a process for obtaining a clear positiveprojected image directly from a negative film, a process for obtaining aclear negative I projected image from a negative film by applying a color-eliminating means to a color-developed projection surface, a processfor effecting a reverse projection and a normal projectionto one and thesame projection surface, and a process by which any dark room is notnecessary to form a color-developed image. With respect tocolor-developed image of the photocolor developing and eliminatingmaterial, many of the photocolor developing and eliminating materialsare usually colorless before color-developing, but some of thephotocolor developing and eliminating materials are colored. Forexample, when a colorless photocolor developing and eliminating materialis irradiated by a radiation having the characteristic absorption range,the colorless material is colorized to form a colored image while acolored photocolor developing and eliminating material becomes colorlessor the color is changed to a different color. Therefore, the termcolor-developed image in this invention means an image formed byirradiating a colorless or colored photocolor developing and eliminatingmaterial by a radiation.

Other object of this invention will be clarified from the detailedexplanations in accordance with the attached diagrams. In the followingparagraphs, the attached diagrams are briefly explained.

FIG. 1 is the respective absorption spectrum curves of the three kindsof photosensitive components which are used for the color imagerecording material of this invention;

FIG. 2 is the absorption spectrum of the photosensitive matter composedof the three kinds of photosensitive components;

FIG. 3 is the diagram showing the spectrum distribution of the positivecolor slide which is the original image;

FIG. 4 is a diagram showing the spectrum distribution of the color imageobtained by exposing the positive color slide of FIG. 3; and

FIG. 5 is a diagram showing the absorption spectrum curve of the stateof color development of the respective kinds of photocolor developingmaterials used in this invention.

FIG. 6 through FIG. 8 show the embodiments of the method of theproduction of a projected image of this invention, and FIG. 6 shows thelight path for forming the projected image by irradiating a negativefilm onto a screen made of the photocolor developing and eliminatingmaterial with ultraviolet light; FIG. 7 shows the light path of the casewhen the image of the negative film is projected on a screen with atungsten lamp, and the screen is irradiated with ultraviolet ray; FIG. 8shows the light path of the case when the visible light, ultraviolet rayor the mixed light thereof is used as the light source.

Generally speaking, a photocolor developing and eliminating materialdevelops color from the colorless state by exposure, i.e., by theirradiation the radiation of a specific range of wave length, or aphotocolor developing eliminating material can change color from thecolored state, and can be reduced into the original state by theirradiation of the radiation of other range of wave length. For examplespiropyran compound is known to be changed into the state having newabsorption in the visible range, i.e., in the photocolor developingstate.

However, the color-developed state can be retained for a certain periodof time (such as several minutes in polystyrene film at a roomtemperature) but it is reduced to the original state (colorless state).

As mentioned above, in accordance with this invention, a new photocolordeveloping and eliminating material whose color-developing state can bestabilized for a long time by taking into consideration the developingand eliminating mechanism through the photocolor developing andeliminating mechanism of the photocolor developing and eliminatingmaterial, and the new photocolor developing and eliminating material isused as the recording material.

It is considered that the conventional photocolor developing andeliminating materials which develop colors by the photo-iondissociation, photo-radical dissociation, photo hydrogen transmission,photosteric structure change, photo-oxidation or the photoreduction orsuch like changes.

Examples of the compounds which photocolordevelop and eliminateaccording to such mechanisms include:

1. Photo-ion dissociating materials a-l. carbinols such as malachitegreen carbinol, crystal violet carbinol,

phenolphthalene carbinol and the like. a-2. cyanides such as orlaminecyanide, brilliant green cyanide, malachite green cyanide, pararoseaniline cyanide, phenol phthalene cyanide and the like,

a-3. sulfides such as crystal violet sulfide, malachite green sulfite,

methyl violet sulfite, para-rose aniline hydrosulfite, rose-anilinesulfite and the like, b. spiropyrans such asl,3,3-trimethyl-indolino-benzopyryl spiran and the derivatives thereof,bispiro-2,2'-(5,6-benzopyran) 5,6-benzopyran-2-spiro-2' B-naphthopyran,3 ,3 -dimethyl-bispiro-2,2 -(B-naphthopyran the like, 2. Photo-radicaldissociating materials such as a. tetrachloro-l (4H) phthalenone,tetrachloro- 1(2) phthalenone and the like, b. hexaphenyl bi-imidazolyl,tetra phenyl pyrole dimer and the like 3. Photo-hydrogen transmittingmaterials a. Anils such as salicylidene aniline, salicylidene metatoluidine, salicylidene orthochloroaniline, salicylidene metaphenylenediamine, 5-bromo salicylidene a-naphthyl amine and the like, b. Aromaticnitro compounds such as 2-( 2,4'-dinitrobenzyl pyridine,4-(2',4-dinitrobenzyl) pyridine 4. Photo steric structure changingmaterials a. Cis-trans transmission materials such as 4,4-dimethyl aminoazobenzene, 4-nitro-4-aminoazobenzene, 4,4-diaminostilbene-2,2'-disulfonic acid, diformyl-4,4-diamino stilbene-2,2'-disulfonic acid and the like.

b. Bianthrones such as xanthylidine anthrone, bianthrone and the like 5.Photo-oxidizing or photo-reducing materials such as methylene blue andthe iron salts, thionine and the iron-salts.

In accordance with this invention, the material having electron orproton donating or accepting properties is added as the color developedstate stabilizer to the photocolor developing and eliminating materials,and the color developed state is stabilized by giving and receiving ofelectron or proton.

The effect of the stabilizer depends on the combination of thephotocolor developing and eliminating substance and the stabilizer,concentration, temperature and the properties of the binder to be addedfor preparing the photosensitive layer or the properties of matrix inwhich dispersing the photocolor developing and eliminating materials isdispersed when the photocolor developing and eliminating materials arecontained in the recording member. Therefore, the specific substancescannot be specified, but the following materials are effective.

As electron donating materials the following can be given.

and

l. 'rr-electron donating materials such as a. benzene and alkylderivatives such as benzene, toluene, xylene and the like.

b. polycyclic aromatic compounds such as naphthalene, anthracene,pyrene, tetracene, perylene and the like 2. n-electron donatingmaterials a. aliphatic amines such as ethyl amine, propyl amine, butylamine, octylamine, and the like b. aromatic amines such as aniline,dimethylaniline,

paraphenylene diamines, and the like As electron accepting materials thefollowing can be given.

I. quinones such as tetracyano quinodimethane (TCNQ) chloroanil, bromoanil, paraquinone, a-naphthoquinone, ,B-naphthoquinone, and the like 2.Nitro compounds such as 2,4-dinitro benzene, 1,3,5-tri-nitrobenzene orthe like As proton accepting materials, the following compounds can begiven,

Acrydine, quinoline, benzylamine, pyridine, diphenylamine, methyl ethylether, azobenzene, chlorobenzene, or the like As the proton donatingmaterials the following compounds can be given.

Phenol, aniline, acetic acid, butyalcohol, crotonic butylalcohol,benzoic acid or the like The above given compounds are effective as thestabilizers, and when combined with the photocolor developing andeliminating materials, the mixture is coated on the supporters such asmetal, paper, plastic or the like, or is coated by dispersing themixture in an appropriate matrix materials to prepare the photosensitivelayer of the recording material, and the mixture dispersed in the matrixis formed in the state of film, and the obtained film is used.

Thus obtained recording material can perform color development and colorelimination by the irradiation of Xray, ultraviolet ray, visible ray,infrared ray and various kinds of radiations.

It is not specified which of photocolor developing wave length orphotocolor elimination is on the side of long wave length.

As mentioned above, in accordance with the method of this invention,when a stabilizer is contained in photocolor developing and eliminatingmaterials, it is possible to retain lastingly the stable colordeveloping state when the radiation of a specific wave range is given tothe materials.

Therefore, when such new materials are used as the main component of therecording material, it is apparent that a recording material which canbe widely used is obtained.

For example, phototyping materials, materials for making master sheetsfor printing, and the recording materials for telecommunication machinesand electronic computers or other recording materials.

For example, when mis-typing is made by the erroneous operation isphototyping, or a part of the phototyped copy is changed because of thecorrection of the original, the photosensitive surface is eliminated, orthe separately corrected typing is replaced for the mistyped portion orthe portion to be corrected by eliminating the photosensitive surface orphototyping is done anew, when the conventional photosensitive materialis used, and therefore the phototyping technique has been remarkablyretarded, as is known to those skilled in the art. However, when thisinvention is employed, such correcting operation can be easily done witha short time by erasing the image by irradiating the radiation forerasing the color of the portion which is to be corrected, and byexposing the corrected image with the radiation for color-development.

Japan this invention is very convenient in phototyping system in Japenwhere the people use a great numher or characters and various kinds ofletters. In other applications of this invention, most of the correctingoperations which require remarkable experiences can be quickly carriedout by making use of the reproduction of the image by means ofreexposure, and the erasing through the radiation stimulus. Thefollowing are the examples to further illustrate the recording materialsto which the stabilizing method of this invention is applied.

EXAMPLE 1 34.4 mg of malachite green cyanide, 20.4mg. oftetracyanoquinodimethane, and 10 g. of ethylcellulose were dissolvedinto g. of alcohol, and the obtained mixture was coated on a transparentglass plate and the coated mixture solution was dried. Thus preparedphotosensitive layer developed bluish green at the quantum yield of 1when irradiated with 313 mu. of mercury lamp ray and the photosensitivelayer could be kept in a stable color developing state and then when 365mu. of mercury lamp ray was irradiated thereto the color thereof waseliminated. The process of color development and color elimination couldbe repeated over and over again.

EXAMPLE 2 10 g. of salicylidene anil, 9 g. of acrydine were uniformlymixed, and thermally melted, and then cooled off. Thus obtained crystalwas crushed, and was finely dispersed into resin, and a film wasprepared. Thus prepared recording material developed yellowish orange bythe irradiation of 365 mu. of mercury lamp ray, and the color developingstate can be stably retained, and then a tungsten lamp was used as thelight source, and the erasing of color could be carried out byirradiating the light rays above 420 mu. by using a filter and tungstenlamp as the light source. The process of color development and colorelimination could be carried out repeatedly.

The following are the explanations about the embodiments in which thesubstance of heterogeneous system belonging to another type, or theintermediate substances between the homogeneous system and heterogeneoussystem were used as the stabilizers.

When the heterogeneous system materials or the intermediate substancesbetween a heterogeneous system material and a homogeneous systemmaterial were used as the stabilizers, as explained in detail, thematerials having stabilizing properties, such as acidic, basic, ionic,electric charge transmitting properties or high surface energy, shouldbe selected as the surface of the solid particles of said materials, orthe surface of said material should be treated so as to give the abovementioned properties to the surface thereof.

In the following, examples of the photocolor developing and eliminatingmaterial systems, heterogeneous system material stabilizers havinginherently a stabilizing surface, the intermediate substances thereof,heterogeneous system material stabilizers subjected to a stabilizingtreatment, intermediate substances thereof, and concrete examples wherethe above-mentioned materials and stabilizers are employed, are shown.

Representative and preferable photocolor developing and eliminatingmaterials in this invention are as follows:

A. Spirans such as 1,3,3-trimethylindolino 6nitrobenzo pyrylspiran6'-nitro-8 -methoxy- 1 ,3 ,3-trimethyl indolino-6 nitrobenzopyrylspiran6'-nitro-8 '-fluoro-l ,3 ,3-trimethylindolino-6'- nitrobenzopyrylspiran6'-8'-dibromol ,3 ,3-trimethylindolino-6- nitrobenzopyrylspiran and thecombinations of spiropyran compounds and hydrogen donors, i.e., protondonating substances such as phenols, organic carboxylic acids, weakinorganic acids and the like. B. Anils such as salicylidene-aniline,salicylidene-m-toluidine,

salicylidene-p-toluidine, salicylidene-orchloraniline,

salicylidene-p-bromoaniline, salicylindene-mbromoaniline,

salicylidene-p-bromoaniline, salicylidene-m-phenylene-diamine,salicylidene-o-anisidine, salicylidene-p-anisidine,salicylidene-m-aminobenzoic acid,

salicylidene-p-aminobenzoic acid,

and the combination of anil compounds and proton accepting materialssuch as acrydine, quinoline and the like,

C. Semicarbazones such as cinnamic aldehyde semicarbazone, m-methoxycinnamic aldehyde semi-carbazone, o-methoxy cinnamic aldehydesemi-carbazone, o-methoxy cinnamic aldehyde phenyl semicarbazone, andthe like.

As the examples of the heterogeneous system material having the surfacefor stabilizing the specific state of photocolor developing andeliminating materials, the

following can be given 1. As solid materials, organic and inorganiccompounds having acidic surfaces, basic surfaces, ionic solid, electriccharge transmitting properties, or high surface energy, and paper,fiber, wood, porcelain, metal, glass, synthetic fiber, resin film or thelike.

2. As gel form materials, for example, substances as shown below orinorganic sol form substances and organic gel form substances containingthe below given individual materials or the like.

The inventors of this invention have found out the fact that it is moreeffective in some cases to treat the surface by using the substanceshaving acidic, basic, ionic, electric charge transmitting, or havinghigh surface energy.

In the following examples of the substances are shown below.

1. As high polymers:

nitrocellulose cellulose acetate ethyl cellulose polyethylenepolystyrene polyvinyl acetate polyvinyl alcohol polyvinyl chloridepolyacrylonitrile polymethylmethacrylate gelatin 2. As the solid acid,Lewis solid acid is used, and the example of Lewis solid acid are asfollows.

natural clay minerals acidic terra abla, clarite bentonite kaolinfullers earth montmorilonite fiuoridine solidified acids such as thoseobtained by adhering sulfuric acid, phosphoric acid onto silica gel oralumina phosphoric acid obtained by using quatz sands as carrier thecalcined compounds of diatomaceous earth and phosphoric acid cationexchange resin silica-alumina, silica-magnesia, silica-boria inorganicchemicals ZnO, A1 0 TiO CeO AS203, V 0 SiO Sb O CaSO MnSo CuSO NiSO CoSOCdSO SrSO MgSO FeSO BaSO KHSO K (NH4)2SO4, A12(SO4):1, 2( 4)3,CY2(SO4)2, Ca(NO 4H O, Bi(NO 5H O, Zn(NO 6H O, Fe(NO 9l-l O, CaCO Zrphosphate, Ti phosphate, AlPo PbCl HgCl CuCl AlCl SnCl CaCl AgCl, H WOAgClO ZnS, CaS, Mg(ClO 3. Lewis solid base is generally used as thesolid base and the examples of the Lewis solid base are as follows,Inorganic chemicals such as CaO, MgO, BeO, SiO ZnO, Na CO K CO Kl-lCO(NH,) CO BaCO KNaCO Na WO 2H O, KCN Those prepared by adhering causticsoda to silica gel,

and those prepared by adhering potassium hydroxide anion exchange resinsnitrous oxide activated carbon, ammonia activated carbon 4. As thesizing agents, rosin, emulsified wax, reinforced sizing agent, bitumenemulsifier, latex, silicon 1. As the liquid matrix, such as benzene,toluene, xylene, cyclohexane, normal hexane, butylalcohol, ethylalcohol, isopropyl alcohol dimethylformamide acetone methyl alcoholethyl acetate ethyl ether pyridine trichlene and the like, or thehomologues thereof. 2. As the solid matrix, the following examples canbe given.

Condensate type polymers such as polyamide type resin,

N-alkyl polyamide,

polyimide,

polypeptide,

polyester type resin, polycarbonate resin,

polyacid anhydride resin, polyether type resin, and the like.

As polymerized type polymers, the following examples can be given.aliphatic hydrocarbon type vinyl resin, aromatic hydrocarbon type vinylresin (polystyrene yp vinyl alcohol type resin, nitrile type resin,acryl type resin, methacryl type resin and the like As the examples ofsuch high polymer substances as above the following can be given.nitrocellulose, cellulose acetate, ethyl cellulose, polyethylene,polystyrene, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride,polyacrylonitrile, vinyl chloride, polymethyl metacrylate, and gelatineand the like.

In addition to the above, oligomer and other single molecular organicsubstances having excellent adherability can be used.

It is also possible to use synthetic photo-color developing materialsobtained by chemically bonding photocolor developing materials to highpolymer or oligomer.

The following are the concrete examples to further illustrate thisinvention.

However, a great number of modifications within the technical scope ofthis invention may be carried out as a matter of course.

EXAMPLE 3 20 mg. of 6-nitro-l,3,3-trimethylindolinobenzopyrylspiran wasdissolved into ml. of toluene, and thus obtained mixture solution wascoated uniformly on the art-treated surface of one sided art paper whosethickness is about 80 t. in such a manner that the coat ing could becomefrom 1 to 2 ,u. to prepare the photocolor developing and eliminatingrecording material.

EXAMPLE 4 20 mg. of 6'-nitrol,3,B-trimethylindolinobenzopyrylspiran wasdissolved into 10 ml. of toluene, and thus obtained mixture was coatedon an aluminum plate whose thickness is about 100 pt. in such a mannerthat the thickness of the coating could become from 1 to 2 1.1.. toprepare a photocolor developing and eliminating recording material.

EXAMPLE 5 5 g. of ethyl cellulose was mixed along with 500 mg. of ethylalcohol and the mixture was sufficiently stirred, and after dissolvingthe same sufficiently the mixture was coated on an art paper, and thecoating was dried.

Thereafter, 20 mg. of 6-nitro-l,3,3-trimethylindolinobenzopyrylspiranwas dissolved into 10 ml. of toluene, and the mixture was coated on theart paper having been coated with the above prepared ethyl cellulose insuch a manner that the thickness of the coating became as thick as 0.5to 1 ,u. to prepare a photocolor developing and eliminating recordingmatter.

EXAMPLE 6 20 mg. of 6'-nitro-l ,3,3-trimethylindolinobenzopyrylspiranwas dissolved into 10 ml. of toluene, and the obtained mixture wascoated on a polystyrene film whose thickness is 100 ,u. to prepare aphotocolor developing and eliminating recording matter.

In the above given examples from 3 through 6, the photocolor developingand eliminating recording material is subjected to exposure and fixationbefore or after drying treatment as is described in the followingparagraphs.

The above prepared photosensitive recording material is subjected to theexposure by using the ultra violet ray obtained by using the light froma 500 W high pressure mercury lamp and the glass filter (UV-D25) at adistance of 10 cm from the light source for about 15 seconds in theExamples from 3 to 5, and for about one minute in Example 4, and forabout 30 seconds in Example 6 and the photosensitive recording materialdeveloped reddish purple and retained stable clear color for more than20 minutes.

When a negative image is placed between the photosensitive member andthe light source, the corresponding positive photocolor image could beobtained.

When thus colorized photosensitive member was subjected to theirradiation of the visible ray obtained by using a glass filter (UV-39)against the light from the light source for 30 seconds, and thecolorizing state was perfectly eliminated. The color developing andeliminating process could be repeated over and over again.

The photosensitive member in the colorized state was treated with 1percent caustic soda aqueous solution, the developed color could befixed.

When thus fixed color image was treated with 5% hydrochloric acidalcohol aqueous solution, and the above mentioned treatment with visiblelight was carried out, and the fixed state was turned back to thephotocolor developing and eliminating state.

EXAMPLE 7 5 g. of kaolin, and 15 ml. of ethylalcohol were sufficientlymixed by using an ultrasonic wave stirer for about 5 minutes, and themixture was coated on a one sided art paper whose thickness is u. insuch a manner that the thickness of coating could become about 10 [.L.thick.

EXAMPLE 8 5 g. of acidic terra abla, and 15 ml. of ethylalcohol weresufficiently mixed for about 5 minutes by using an ultrasonic wavestirer, and the obtained mixture was coated on two sided art paper(whose thickness is 80 p.) in such a manner that the thickness of thecoating could become as thick as about 10 u.

EXAMPLE 9 g. of kaolin, 0.02 g. of ethyl cellulose, 15 ml. of di oxanewere sufficiently mixed for about minutes by using an ultrasonic wavestirer, and the obtained mixture was coated on two sided art paper whosethickness is about 100 pt. in such a manner that the thickness of thecoating could become about u.

EXAMPLE l0 5 g. of bentonite, and 15 ml. of ethyl alcohol, weresufficiently mixed for about 5 minutes by using an ultrasonic wavestirer, and the obtained mixture was coated on an aluminum plate of 100,u.. thick in such a manner that the thickness of the coating couldbecome EXAMPLE 1 l 5 g. of kaolin, ml. of ethyl alcohol, and 20 mg. of6-nitro-l ,3,3-trimethylindolinobenzopyrylspiran were sufficiently mixedfor about 5 minutes by using an ultrasonic wave stirer, and then theobtained mixture was coated on an art paper, aluminum plate or a glassin such a manner that the coatings could become as thick as about 10 p"As described so far in the preceding paragraphs, the resultingstabilized color developed image on the recording material was fixed asa permanent image, and the fixed image is turned back to the originalimage, and the following is an explanation about the method therefor.

In accordance with this invention, as described above, the colorizedimage is retained as a permanent latent image by the treatment by basicmaterial or anion as the stabilizer, and then the fixed image is turnedback to the photoreversible colorized image by treating the fixed imagewith acidic material or cation as a restoring agent.

As the examples of the fixing agents for fixing the colorized image, thefollowing can be given, inorganic base such as sodium hydroxide,potassium hydroxide and the like, and ammonia, and amino compounds suchas ethylamine, propyl amine, butyl amine and the like, and potassiumcyanide, sodium cyanide, or such like salts or a weak acid and a strongbase, Bronsted base and the salts thereof may be used.

As the restoring agents, for example, organic acids such as acetic acid,benzoic acid and the like, and inorganic acids such as hydrochloricacid, nitric acid and the like, Lewis solid acid and such like acids maybe used.

The recording material is treated with these in liquid state of gaseousstate.

The following is an explanation about the examples of the fixing of thephotosensitive material and the method for restoring the photocolordevelopment and elimination property, but it is a matter of course thata great number of modifications can be done within the scope of thisinvention.

EXAMPLE 12 68 mg. of 6'-nitro-l,3,3-trimethylindolinobenzopyrylspiran,36 mg. of p-nitrophenol, 10 g. of polystyrene were dissolved in g. ofxylene, and the mixture was coated on a transparent glass plate anddried to prepare a recording material.

Thus obtained photosensitive layer was developed into red color byirradiating ultraviolet ray by using a 250 W ultra high pressure mercurylamp, and Toshiba Filter UVD-25 at a distance of 10 cm from the lightsource for 30 seconds, and it was kept in a stable colorized state forabout 60 hours.

Next, by using a Toshiba Filter UV-39, visible light was irradiatedthereto for 30 seconds at the same distance from the light source, andthe colorized state was perfectly eliminated, and the color developingand eliminating process could be carried out repeatedly.

The recording material in the colorized state was treated with 10%ammonia alcohol aqueous solution (3 parts by volume of ethyl alcohol,and 7 parts by volume of water), and the developed color could be fixed.

Thus fixed color was treated with 5% hydrochloric acid alcohol aqueoussolution and the fixed state was restored to the original photocolordeveloping and eliminating state.

EXAMPLE l3 59 mg. of 6-nitro-l,3,3-trimethylindolinobenzopyrylspiran and10 g. of ethyl cellulose were dissolved into ethyl alcohol aqueoussolution (containing 9 parts by volume of ethyl alcohol and one part byvolume of water), and the obtained mixture was coated on a glass plate,and dried, and thereafter the coating was peeled off, and a transparentfilm was obtained.

Thus obtained film was subjected to color development into purplishcolor by the irradiation of ultraviolet ray obtained by the combinationof a 250 W ultra high pressure mercury lamp and Toshiba glass Filter UVD-25 at a distance of 10 cm from the light source, and the colorizedstate was retained at a room temperature for more than 20 minutes in adark place, and when it was irradiated with visible light, it waseliminated right away.

Thus obtained colorized state was fixed as yellow color developed stateby the treatment of 5% sodium hydroxide alcohol aqueous solution.

The fixed colorized state was treated with 10% acetic acid alcoholaqueous solution, and it was stabilized in yellowish orange colordeveloped state, but when visible light was irradiated thereto by usingthe same light source and Toshiba Filter UV-39 at the same distance, itwas eliminated and turned back to the original state.

It is possible to carry out the process of colordevelopment-fixation-stabilization-elimination can be repeatedsubstantially without any fatigue.

The following is an explanation about the embodiment of of a colorrecording member in which the new photocolor developing and eliminatingmaterial for forming a color image directly on the recording material isused.

The photocolor developing and eliminating materials used for the colorrecording member of this invention are preferably spiropyran compoundsas given above, or the mixture of the above given compounds and thehydrogen donating materials i.e. proton donating materials, such asphenols, as the stabilizers, anils or the mixture of anils and protonaccepting materials such as quinoline, and semicarbazones.

Such photocolor developing and eliminating materials have respectivelythe specific absorption wave length ranges.

This is explained in accordance with FIG. 5. In FIG. 5, the horizontalaxis represents wave length of the radiation to be irradiated onto thephotocolor developing and eliminating material, and the vertical axisrepresents the ratio of absorption. For example, cinnamic aldehydesemicarbazone in FIG. a) has the absorption spectrum range (shown by thesolid line in FIG. 5) in such a wave length range that is shorter than400 mp i.e., in ultraviolet ray portion.

When ultraviolet ray is irradiated onto this compound, the absorptionrange is generated in the visible range (the curve shown by the dottedline in FIG. 5).

In FIG. 5 almost blue absorption is shown, and therefore said materialdevelops the complementary color of blue color.

In the same manner as is apparent from the diagrams from FIG. 5 b d,N-salicylidenem-toluidine, N-4- methylsalicylidene aniline,N-salicylidene aniline and the like have the respective specificabsorption wave length ranges in ultraviolet ray portions, and absorbthe light of said wave length ranges, and come to have the specificabsorption wave length ranges in the respective visible ranges, and therespective complementary colors are developed.

The color recording member of this invention can be prepared bydispersing at least one kind of the above mentioned photocolordeveloping and eliminating materials therein in the form of matrix, andas the high polymers as the dispersing agents, the following materialscan be given.

I. As the examples of condensate type high polymers;

polyamide type resin, N-alkylpolyamide, polyimide, polypeptide,polyester type resin polycarbonate resin, polyacid anhydride resin,polyether type resin 2. As polymer type high polymers;

aliphatic hydrocarbon type vinyl resin, aromatic hydrocarbon type vinylresin (polystyrene yp vinyl alcohol type resin, nitrile type resin,acryl type resin, methacryl type resin,

As the examples of such high polymer materials as given above, thefollowing can be given;

nitrocellulose cellulose acetate ethyl cellulose polyethylenepolystyrene polyvinyl acetate polyvinyl alcohol polyvinyl chloridepolyacrylonitrile polyvinyl chloride polymethylmethacrylate gelatin andthe like In addition to the above, oligomer or other monomer organicsubstances having excellent bonding property may be used.

It is also possible to use synthetic photocolor developing materialsprepared by chemically bonding photocolor developing materials to highpolymers or oligomers.

The examples of liquid dispersing agents include benzene, toluene,xylene, cyclohexane, normal hexane,

' butyl alcohol, ethyl alcohol, methyl alcohol, isopropyl alcohol,dimethyl formamide, acetone, ethyl ether, ethyl acetate and thehomologues.

When photocolor developing and eliminating materials are dispersed intoa dispersing agent in the form of matrix, the absorption wave lengthranges in visible light range at the color developed state depend onkinds of the dispersing medium.

This is explained in accordance with the diagrams FIG. 5 e, f, g, h.

For example, when 8'-carboxy-l ,3,3-trirnethylindolinobenzopyrylspiranis used as the photocolor de veloping and eliminating material, andacetone solution, methyl alcohol solution, and propyl alcohol solutionare used as the dispersing medium as is shown in the diagrams FIG. 5(e-l) through (e-3), the absorption wave length of the visible rangecomes to be different in the color developed state. In other words, inthe solution of an acetone dispersing agent the absorption wave lengthrange is present in about green color portion (see the diagram (e-1)),and in methyl alcohol dispersing agent, the absorption wave length rangeis present in about blue portion (see the diagram (2-2)).

The color recording member of this invention may be prepared in thefollowing manner.

1. One or more than one layer of photosensitive component or one or morethan one kind of photosensitive component (i.e., photocolor developingand eliminating material or the mixture of the same and the stabilizers)is uniformly coated on the transparent or nontransparent supporter.

2. One or more than one layer of photosensitive component or one or morethan one kind of photosensitive component is uniformly dispersed intothe dispersing medium without a support to prepare the photosensitivematerial.

The following is an explanation about the process for recording theimages.

I. When photocolor developing and eliminating materials containingphotochromic substances are used: when spiropyran compounds or themixture of spiropyran compounds and stabilizers, are used, the recordingmaterial is, in advance, wholly exposed to photocolor developing lightsuch as ultraviolet ray to make it sensible to the light of the wholevisible range, and the resulting recording material is subjected to thecolor image exposure, and the recording is carried out by using aphotocolor eliminating process. It is possible to repeat a step oferasing the recorded image by light, a step of restoreing the same tothe original totally colorized state, and a step of recording again.

By treating the photosensitive materials which are prepared by thecombination of spirans by an aliphatic amine such as hexyl amine or astrong alkali such as caustic potassium, the image thereon ispermanently stabilized in the form of yellow latent image, and when itis treated with an organic acid and an inorganic acid, it may be turnedback to the original color image.

2. The case in which a thermal color developing and photocoloreliminating materials containing photochromic substances:

1. The combinations of the above given spirans with phenols, organiccarboxylic acids, and strong acids (mineral acids) 2. 1,3,3-trimethylindolino-8 '-carboxybenzopyrylspiran and semi-carbazones(refer to item C above) When the group of materials in l) and 2) aboveis used, ultraviolet ray and heat are used in advance to the effect thatthe color is developed so as to make the recording member sensible tothe whole visible range, and then a color image exposure is carried out,and the elimination is carried out in accordance with the exposedportion, and a positive color image is recorded.

Thus obtained recorded image can be turned back to the original totallycolorized state by means of heat and ultraviolet ray irradiation to theeffect that the image can be erased, and this operation can be carriedout repeatedly.

When the photosensitive materials obtained by the combination ofspirans, are used, the yellow latent image can be permanently stabilizedby treating the same with amine such as hexyl amine or a potassiumhydroxide solution. When it is further treated with an acid, it can beturned back to the original color image.

The following are the concrete examples of this invention. It is amatter of course that a great number of other modifications within thescope of the technical idea of this invention can be carried out.

First, the following Example 14 refers to an example of a colorrecording member having the absorption range covering the whole visiblelight range prepared by selecting appropriately the dispersion mediumand the additive into which one and the same photocolor developing andeliminating material is dispersed and incorporating them to thephotosensitive layer.

EXAMPLE l4 l,3,3 trimethylindolino-6 '-nitrobenzo pyrylspiran 60 mg.polystyrene l() g. A xylene 50 cc. l ,3,3-trimethylindolino-6'-nitrohenzopyryl spiran 60 mg. p-nitrophenol 40 mg. B polystyrene l gxylene 50 cc. l,3,3-trimethylindolino-6' nitrohenzopyrylspiran 60 mg.malonic acid 40 mg. polystyrene 10 g. C benzene 50 cc.

The respective mixtures A, B and C were coated sequentially on glassplates uniformly and the resulting coating was dried, and a three layertransparent film was prepared and thus prepared transparent film wasused as the photosensitive material.

Or, the mixtures A, B, and C were separately sprayed on a supporter suchas polyester transparent support or a paper to prepare a photosensitivematerial.

The color image recording was carried out in such a manner that theabove prepared photosensitive materials were placed at a distance .ofabout 50 cm from the light source and by using a 500 W mercury lamp asthe light source and a visible light out filter (Toshiba glass FilterUV-D 25) the total exposure was carried out for 10 seconds to have thephotosensitive material sensitized in the whole visible light range, andthen, the color image was exposed from the distance of 50 cm for 10seconds by using a 250 W tungsten lamp, the color developing materialwas eliminated of the colors corresponding to the color developingmaterial, and a positive color image could be obtained.

Next, when the positive color image was dipped in a 10 percent aqueoussolution of potassium hydroxide, the color image was changed into yellowlatent image and is stabilized permanently. When it was again dipped inthe solution of acetic acid, it could be again changed into color image.

FIG. 1 shows the absorption spectra of the respective photosensitivematerials A, B, and C of the above example (the horizontal axis showingthe wave length A by my.) and FIG. 2 shows the absorption spectrum ofthe photosensitive material composed of the three layers A, B and C asmentioned above.

When the positive color slide of the spectrum distribution shown in FIG.3 was exposed in the same manner as above, the positive color image ofFIG. 4 could be obtained.

The following Example 15 refers to an example of a color recordingmember comprising a photosensitive layer including more than one ofphotocolor developing and eliminating materials uniformly mixed and madeinto one layer.

EXAMPLE l5 N-salicylidene aniline l0 g A acrylidine l() g. 8-carboxyl.3,3 trimethylindolinobenzopyrylspiran 60 mg.

B ethylcellulose 10 g 6'-nitro8'methoxy-1,3,3-trimethylindolinobenzopyrylspiran 60 mg.

C polystyrene 10 g The following is an explanation about the method forpreparing the A, B, and C.

A: 10 g. of N-salicylidene aniline and 10 g of acrylidine are thermallymelted at C, and the hot mixture is abruptly cooled off, and then finelycrushed.

B: 60 mg. of 8'-carboxy-l ,3,3-trimethylindolinobenzopyrylspiran and 10g. of ethyl cellulose are dissolved into 50 cc. of alcohol and then themixture solution is finely crushed after having dried the same.

C: 60 mg. of 6'-nitro-8'-methoxy-l,3,3-trimethylindolinobenzopyrylspiranand 10 g. of polystyrene and dissolved into 50 cc. of xylene, and thepowders A and B are dispersed thereinto and the obtained mixture iscoated on a paper support and the coating is thermally dried to preparea photosensitive material.

The color image recording material was totally irradiated for 10 secondswith ultraviolet ray by using a 500 W mercury lamp and thermalcolor-development was carried out for about one minute at a temperatureranging from 50C to 60C by using a heater or heat ray so that the wholevisible range could be sensitized.

Next, the color image was exposed for 10 seconds at a distance of 50 cmby using a positive color slide and a 250 W tungsten lamp, and the colorelimination was carried out in accordance with the sensitized portion,and a positive color image could be recorded.

Thus obtained recorded image can be erased by turning the same into theoriginal colorized state by heat and the irradiation of ultraviolet ray,and this operation can be effected repeatedly.

As described so far, the structure of the color recording material ofthis invention is that a photosensitive material is dispersed into atransparent or semitransparent dispersing material, and thephotosensitive material is used in the form of film or plate, or thephotosensitive material is made into a single layer or multilayer, andis adhered on a plane support such as film, paper, metal, or glass.

In addition to the above, photosensitive material is used in the form ofthin layer on the support without using the dispersing agent, and atransparent high polymer film is coated on said thin film to make thecolor recording material of this invention.

In the color recording member of the following Example lSA, more thanone of photocolor developing and eliminating materials are used and eachof them has each individual absorption range in the colordevelopedstate, and further the dispersion medium and the additive areappropriately selected and incorporated to a photosensitive layer insuch a manner that the absorption range covers the whole visible lightrange.

EXAMPLE 1 5A 1,3,3-trimethylindolino-6'-nitrobenzopyrylspiran 60 mg.Malonic acid 40 mg.

A Polystyrene l0 g. Benzene 50 cc. 8'-carboxy-l,3,3-trimethylindolinobenzopyrylspiran 60 mg.

B Ethylcellulose 10 g. 6'-nitro-8 '-methoxy lv3,3-trimethylindolinobenzopyrylspiran 60 mg.

C Polystyrene 10 g.

A, B, and C above are sequentially coated on a glass plate uniformly anddried to form a three-layer transparent film which is used as aphotosensitive material. Or, A, B and C are separately scattered on asupport such as a polyester transparent support or paper to form aphotosensitive material. Color image recording is carried out by usingthe resulting photosensitive material in a recording member. The wholesurface of the recording member is exposed to a ultraviolet lightobtained by passing a light from a 500 W mercury lamp through a visiblelight cut filter (Toshiba Glass Filter UV-DZS) for 10 seconds at adistance of about 50 cm. from the light source to sensitize therecording member for the whole visible light range. The recording memheris then exposed to a color image of a positive color slide by using atungsten lamp (250 W) at a distance of 50 cm. for 10 seconds and thecolor-developed member corresponding to each color is eliminated to formthe positive color image. Further, the recording member thus treated issoaked in a 10 percent solution of potassium hydroxide to change thecolor image to a yellow latent image which is everlastingly stabilized.When the latent image is treated with an acetic acid solution to producethe color image again.

The following is an explanation about the concrete examples of a newmethod for optionally forming nor mal image and a reversal image, inaccordance with the demand, by using a recording material in whichphotocolor developing and eliminating materials are used.

In regard to the photocolor developing and eliminating materials,stabilizers, dispersing mediums and such like recording materials whichwere used in the following examples, those which have already been givenin the preceding paragraphs were used in the following examples.

EXAMPLE 16 68 mg. of 6'-nitro-1,3,3trimethylindolinobenzopyrylspiran, 36mg. of p-nitrophenol, and 10 g. of polystyrene were dissolved into 50 g.of xylene, and the obtained mixture was coated on a transparent glassplate, and the coating was dried, and peeled off to obtain a transparentfilm, and this transparent film was used as the recording material.

Thus obtained photosensitive layer was subjected to the irradiation ofultraviolet ray for 30 seconds by using a 250 W ultra-high pressuremercury lamp and a Toshiba Glass Filter UVD-25 at a distance of 10 cmfrom the light source, and thus the photosensitive layer presented redcolor, and the photosensitive layer was kept at the stable colorizedstate for about hours.

Next, visible light was irradiated for 30 seconds at the same distancefrom the light source by using a Toshiba Glass Filter UV -39, and thecolorized state was perfectly eliminated. The process of colordevelopment and elimination can be effected repeatedly.

The recording material which was in the above mentioned colorized statewas treated with 10% ammonia alcohol aqueous solution (containing 3parts by volume of ethyl alcohol and 7 parts by volume of water),thereby the developed color could be fixed.

When thus obtained fixed color image was treated with 5% hydrochloricacid alcohol aqueous solution, the fixed state was turned back to theoriginal photocolor developing and eliminating state.

The ultraviolet ray obtained by passing the light of a 250 W ultra-highpressure mercury lamp through a Toshiba Glass Filter UVD-25 wasirradiated for about 30 seconds at a distance of about 10 cm from thelight source through the same filter as above, and thermal colordevelopment was carried out by a heater or heat ray at a temperaturefrom 50C to 60C for one minute to that the whole visible range wassensitized.

Next, a positive image was exposed for 10 seconds at a distance of 30 cmto the light source composed of a 250 W tungsten lamp, and coloreliminated positive image was formed in accordance with the exposedportion.

Thus obtained recorded image was turned back to the original totallycolorized state by heat and the irradiation of ultraviolet ray to theeffect that the image could be erased, and this operation could becarried out repeatedly.

When the photosensitive material obtained by the combination of spiransis treated with amines such as hexylamine or a solution of potassiumhydroxide, thereby the permanent stabilization of yellow latent imagecould be attained.

Thus obtained latent image could be turned back to the original image bytreating the same with acid.

EXAMPLE 17 l ,3 ,3-trimethylindolino-6 -nitrobenzopyrylspiran 60 mg.polystyrene 10 g. A xylene 50 cc. l,3,3trimethylindolino-6'-nitrobenzopyrylspiran 60 mg.

. B p-nitrophenol 40 mg. polystyrene l g. xylene O ccvl,3,3-trimethylindolino-6'-nitrobenzopyrylspiran 60 mg. Malonic acid 40mg. C polystyrene l() g. benzene 50 cc.

A, B, and C were respectively coated uniformly on a glass plate, andthen the coating was dried, and a three layer transparent film wasprepared. Thus prepared transparent film was used as the photosensitivematerial.

Or, A, B, and C were separately coated on a polyester transparentsupport, or paper or such like support by spraying the same to preparethe photosensitive materials.

The color image recording was carried out in such a manner that theabove prepared photosensitive materials were subjected to the totalexposure for IO seconds with ultraviolet ray obtained by using a 500 Wmercury lamp and a visible light cut filter (a Toshiba Glass FilterUV-D25) at a distance of about 50 cm from the light source, so that thewhole visible range was sensitized, and then a color image was exposedthereonto for seconds at a distance of 50 cm from the light source of a250 W tungsten lamp, and the color developed materials corresponding tothe respective colors were eliminated of the colors, and a positivecolor image could be obtained. The positive color image was dipped in a10% aq. solution of potassium hydroxide and then was changed to a yellowlatent image and thereby permanently stabilized. Thus stabilized imagewas changed into a color image by dipping the same in a solution ofacetic acid.

EXAMPLE l8 N-sulicylidene aniline 10 g.

acrylidine 10 g. 8-carboxyl-l,3,3-trimethylindolinobenzopyrylspiran 60mg. B ethylcellulose 10 g.6'-nitro-8-methoxy-l.3,3-trimethylindolinobenzopyrylspiran 60 mg. C

polystyrene l0 g.

An explanation about the method for preparing the A, B, and C isdescribed below.

A: 10 g. of N-salicylidene aniline, 10 g. of acrylidine are thermallymelted, rapidly cooled, and then finely crushed.

B: 60 mg. of 8-carboxy-l,3,3-trimethylindolinobenzopyrylspiran and 10 g.of ethylcellulose were dissolved into 50 cc. of alcohol, and then themixture solution was dried into powder.

C: 60 mg. of 6-nitro-8'-methoxy-l,3,3-trimethylindolinobenzopyrylspiranand 10 g. of polystyrene were dissolved into 50 cc. of xylene, and thenthe powders A and B were dispersed therein, and the mixture was coatedon a paper support, and then the coating was dried by heating and thephotosensitive material was prepared.

The color image recording was carried out in such a manner that thewhole surface was subjected to the irradiation of ultraviolet ray for 10seconds by using a 500 W mercury lamp, and the thermal colordevelopmentwas carried out at a temperature from 50C to C for one minute by using aheater or heat ray, and the whole visible range was sensitized. Next, acolor image was exposed for 10 seconds by using a 250 W tungsten lamp atadistance of 50 cm from the light source, and the color was eliminatedin accordance with the exposed portion, and a positive color image wasrecorded. Thus obtained positive color image could be turned back to thetotally colorized state by heat and the irradiation of ultraviolet rayto the effect that the image could be erased, and this operation couldbe carried out repeatedly.

Next, the following is an explanation in accordance with the attacheddiagrams about the concrete examples of the new image forming method inwhich a screen prepared from the photocolor developing and eliminatingmaterial is used.

First, the following are the examples for forming the screen of thephotocolor developing and eliminating materials applied to the method ofthis invention.

a. 60 mg. of l,3,3-trimethylindolino-6-nitrobenzopyrylspiran isdissolved into 50 ml. of toluene, and thus obtained mixture is uniformlycoated on a high quality art paper and a screen was obtained.

b. 60 mg. of l,3,3-trimethylindolino-6'-nitrobenzopyrylspiran and 2 g.of polystyrene are dissolved into 50 ml. of toluene, and thus obtainedmixture is uniformly coated on a cotton cloth to form a screen.

The following is an explanation in accordance with the diagrams fromFIG. 6 through FIG. 8 about the concrete examples in which the aboveprepared screens were used.

EXAMPLE 19 (FIG. 6)

The screen 16 prepared by using the photocolor developing andeliminating material prepared in accordance witha) or b) above, wasused.

The ultraviolet ray obtained by passing the light form the light source1 1 (500 W ultra-high pressure mercury lamp) through a visible light cutfilter 12, was projected to a negative slide or negative cine film 13,and the light having passed therethrough was condensed by the condenserlens 14, and was sent to the projector lens 15, and the image wasprojected on the screen 16.

Light passed through the bright portion or the transparent portion ofthe negative film l3 and the color was developed at the portioncorresponding to the screen surface 16 and the reversal projected imagewas obtained on the negative film. In particular, in carrying out aslide projection, it is effective to apply visible light from the lightsource 11 when the image is changed in order to quicken the eliminationof the after image as the image to be projected is exchanged.

In carrying out the slide projection, when the degree of the projectionon the screen surface 16 arrives at a certain degree, the projectedimage can be retained even when the excited light is not appliedfurther, and

therefore it is not necessary to carry out continuous exposure.

EXAMPLE 20 (FIG. 7)

The ultraviolet ray obtained by passing the light from the two lightsources 27 (respectively two 250 W ultrahigh pressure mercury lamps)through the visible light cut filter 28, was projected from the frontside onto the screen 26 prepared in accordance with a) or b) above, andthe color was developed on the whole surface of the screen 26.

The visible light obtained from a 250 W tungsten lamp 21 was projectedonto a positive slide or positive cine film 23, and the light havingpassed therethrough was condensed by a condenser lens 24, and was sentto the projector lens 25, and the image was projected onto the screen26.

The portion of the screen where the visible light had arrived waseliminated of the color, and the positive image corresponding to thepositive film was obtained.

In erasing the image, only ultra-violet ray alone excluding visiblelight was irradiated, it was reverted to the totally colorized state.

EXAMPLE 21 (FIG. 7)

The ultraviolet ray light sources 27 and 28 for totally coloring thewhole surface of the screen in Example 20, were placed behind the screenas is shown by the dotted line of FIG. 7, and the irradiation wascarried out from behind. The positive image projection was carried outin the same manner as in Example 20.

EXAMPLE 22 (FIG. 8)

Preparation of screen:

60 mg. of 1,3,3-trimethyl-indolino-8-carboxybenzopyrylspiran wasdissolved into 10 ml. of water, and the resuting solution was added tothe solution obtained by dissolving 10 g. of polyvinyl alcohol into 40ml. of water, and the whole mixture was sufficiently stirred.

Thus obtained mixture was uniformly coated and extended on a cottoncloth, and the surface of the film was colored in red brown color in thenormal state, and thus obtained screen 36 was used, and in the samemanner as in the embodiment of FIG. 8, the projection was carried out.

The light source as the means for eliminating the color can be visiblelight, ultraviolet ray or the mixture of visible light and ultravioletray.

The ultraviolet ray obtained by passing the light from a 250 W tungstenlamp 31 or a 500 W ultra-high pressure mercury lamp 31 through a visiblelight out filter 32, was projected to a positive slide or positivecinefilm 33, and the light having passed therethrough was condensed bythe condenser lens 34, and the condensed light was sent into theprojector lens 35, and was projected onto the screen 36.

The portion on the surface of the screen where the light has arrived,was eliminated of the color, and the positive projected imagecorresponding to the positive film, was obtained.

What is claimed is:

l. A process which comprises irradiating a recording member including inthe photosensitive layer a photochromic material selected from the groupconsisting of carbinols, cyanides, sulfides, spiropyrans, anils,nitrobenzyl pyridines, azobenzenes, stilbene and bianthrones by at leastone radiation through an original image pattern to form an image on therecording member and treating the resulting image with a basic materialor an anionic material selected from the group consisting of sodiumhydroxide, potassium hydroxide, ammonia and amino compounds to fix saidimage as a permanent image, said photochromic material having a propertythat when irradiated by a radiation of a specific absorption wavelengthrange, it obtains an absorption wavelength in the visible light region,thereby being color-developed and the color-developed state iseliminated when irradiated by a radiation of a wavelength rangedifferent from that of the previously applied radiation.

2. A process which comprises irradiating a recording member including inthe photosensitive layer a photochromic material selected from the groupconsisting of carbinols, cyanides, sulfides, spiropyrans, anils,nitrobenzyl pyridines, azobenzenes, stilbene and bianthrones, by atleast one radiation through an original image pattern to form an imageon the recording member and treating the resulting image with a basicmaterial or an anionic material selected from the group consisting ofsodium hydroxide, potassium hydroxide, ammonia and amino compounds, tofix said image as a permenent image, and then the image surface of therecording member is treated by an acidic material or a cationic materialselected from the group consisting of acetic acid, benzoic acid,hydrochloric acid, nitric acid and solid Lewis acids to restore thepermanent image surface to the color-developed image surface, saidphotochromic material having a property that when irradiated by aradiation of a specific absorption wavelength range, it obtains anabsorption wavelength range in the visible light region, thereby beingcolor-developed and the color-developed state is eliminated whenirradiated by a radiation of a wavelength range different from that ofthe previously applied radiation.

3. A color recording process which comprises applying a blanketirradiation of ultraviolet ray or heat to a photochromic recordingmember having a photosensitive layer containing a photochromic materialhaving a visible light absorption spectrum peak in the colored statepresent at 400500 ;L, a photochromic material having a visible lightabsorption spectrum peak in the colored state present at 500-600 u and aphotochromic material having a visible light absorption spectrum peak inthe colored state present at 600-700 ;1., color developing all of thephotochromic materials, selectively eliminating the color of the coloredphotochromic materials corresponding to each absorption spectrum byapplying color light image thereto, thereby producing a colored image.

4. The color recording process according to claim 3 wherein eachphotochromic material is uniformly dispersed in the photosensitivelayer.

5. The color recording process according to claim 3 wherein eachphotochromic material is separately formed in a layer and the resultingthree layers are laminated to form a photosensitive layer.

6. A color recording process according to claim 3 wherein one or more ofthe reagents contains a photochronic compound and a color control agentwhich shifts the natural color elimination absorption peak of thephotochromic compound.

7. A color recording process according to claim 6 wherein the colorcontrol agent is a film-forming mate-

1. A PROCESS WHICH COMPRICES IRRADIATING A RECORDING MEMBER INCLUDING INTHE PHOTOSENSITIVE LAYER A PHOTOCHROMATIC MATERIAL SELECTED FROM THEGROUP CONSISTING OF CARBINOLS, CYANITES, SULFIDES, SPIROPYANS, ANILS,NITROBENZYL PYRIDINED, AZOBENZENES, STILBENE AND BIATHRONES BT AT LEASTONE RADIATON THROUGH AN ORGINAL IMAGE PATTERN TO FORM AN IMAGE ON THERECORDING MEMBER AND TREATING THE RESULTING IMAGE WITH A BASIC MATERIALOR AN ANIOONIC MATERIAL SELECTED FROM THE GROUP CONSISTING OF SODIUMHYDROXIDE, POTASSIUM HYDROXIDE, AMMONIA AND AMINO COMPOUNDS TO FIX SAIDIMAGE AS A PERMENENT IMAGE, SAID PHOTOCHROMIC MATERIAL HAVING A PROPERTYTHAT WHEN IRRADIATED BY A RADIATION OF A SPECIFIC ABSORPTION WAVELENGTHRANGE, IT OBTAINS AN ABSORPTION WAVELENGTH IN THE VISIBLE LIGHT REGION,THEREBY BEING COLOR-DEVELOPED AND THE COLORDEVELOPED STATE IS ELIMINATEDWHEN IRRADICATED BY RADIATION A WAVELENGTH RANGE DIFFERENT FROM THAT OFTHE PREVIOUSLY APPLIED RADIATION.
 2. A process which comprisesirradiating a recording member including in the photosensitive layer aphotochromic material selected from the group consisting of carbinols,cyanides, sulfides, spiropyrans, anils, nitrobenzyl pyridines,azobenzenes, stilbene and bianthrones, by at least one radiation throughan original image pattern to form an image on the recording member andtreating the resulting image with a basic material or an anionicmaterial selected from the group consisting of sodium hydroxide,potassium hydroxide, ammonia and amino compounds, to fix said image as apermenent image, and then the image surface of the recording member istreated by an acidic material or a cationic material selected from thegroup consisting of acetic acid, benzoic acid, hydrochloric acid, nitricacid and solid Lewis acids to restore the permanent image surface to thecolor-developed image surface, said photochromic material having aproperty that when irradiated by a radiation of a specific absorptionwavelength range, it obtains an absorption wavelength range in thevisible light region, thereby being color-developed and thecolor-developed state is eliminated when irradiated by a radiation of awavelength range different from that of the previously appliedradiation.
 3. A color recording process which comprises applying ablanket irradiation of ultraviolet ray or heat to a photochromicrecording member having a photosensitive layer containing a photochromicmaterial having a visible light absorption spectrum peak in the coloredstate present at 400-500 Mu , a photochromic material having a visiblelight absorption spectrum peak in the colored state present at 500-600Mu and a photochromic material having a visible light absorptionspectrum peak in the colored state present at 600-700 Mu , colordeveloping all of the photochromic materials, selectively eliminatingthe color of the colored photochromic materials corresponding to eachabsorption spectrum by applying color light image thereto, therebyproducing a colored image.
 4. The color recording process according toclaim 3 wherein each photochromic material is uniformly dispersed in thephotosensitive layer.
 5. The color recording process according to claim3 wherein each photochromic material is separately formed in a layer andthe resulting three layers are laminated to form a photosensitive layer.6. A color recording process according to claim 3 wherein one or more ofthe reagents contains a photochronic compound and a color control agentwhich shifts the natural color elimination absorption peak of thephotochromic compound.
 7. A color recording process according to claim 6wherein the color control agent is a film-forming material in which thephotochromic compound is distributed.
 8. A color recording processaccording to claim 6 wherein the color control agent is a solvent forthe photochromic compound.
 9. A color recording process according toclaim 6 wherein the photochromic compound is distributed in a matrixcontaining a film-forming material and a solvent for the photochromiccompound miscible with the film-forming material and, if desired, anadditive compound which acts as a color control agent, all suchcompounds contributing to the determination of the color eliminationabsorption peak of the photochronic compound.
 10. A color recordingprocess according to claim 9 containing three or more photochromicreagents of different color elimination absorption peaks in a singlephotosensitive layer, said components assisting in determining thespread of the resulting color elimination absorption spectrum of thelayer so that it substantially covers the visible spectrum.
 11. A colorrecording process according to claim 3 wherein the photosensitive layercomprises three superposed sub-layers each having a differentcharacteristic color elimination absorption spectrum and cooperatingwith the other layers to substantially cover the visible spectrum.